CN111081956B - Ceramic coating diaphragm and preparation method thereof - Google Patents
Ceramic coating diaphragm and preparation method thereof Download PDFInfo
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- CN111081956B CN111081956B CN201911358039.XA CN201911358039A CN111081956B CN 111081956 B CN111081956 B CN 111081956B CN 201911358039 A CN201911358039 A CN 201911358039A CN 111081956 B CN111081956 B CN 111081956B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The application discloses a ceramic coating diaphragm and a preparation method thereof. The ceramic coating diaphragm comprises a base film and a ceramic coating coated on at least one surface of the base film, wherein the ceramic coating adopts a two-component reaction type adhesive with the glass transition temperature of more than 120 ℃. According to the ceramic coating diaphragm, the ceramic coating is formed by the double-component reaction type binder with the glass transition temperature of more than 120 ℃, and the cross-linked network structure of the double-component reaction type binder can reduce the permeation and swelling of electrolyte to the binder, so that the peel strength of the ceramic coating diaphragm is improved; the high glass transition temperature of the glass transition temperature of more than 120 ℃ enables the adhesive to keep certain mechanical strength at high temperature, so that the ceramic coating is not easy to deform, and the high-temperature thermal shrinkage of the diaphragm is reduced. The ceramic coating diaphragm of the application solves the problem of powder falling of the ceramic coating and potential safety hazards caused by the powder falling of the ceramic coating, and improves the use safety of the lithium battery.
Description
Technical Field
The application relates to the field of battery diaphragms, in particular to a ceramic coating diaphragm and a preparation method thereof.
Background
The lithium ion battery has the advantages of high energy density, strong heavy-current discharge capacity, high rated voltage, long cycle life and the like, and the cycle life can reach 3000-5000 times in a shallow charge-discharge mode. The method is widely applied to a plurality of industries and fields of digital products, electric bicycles, electric motorcycles, electric automobiles, electric energy storage, communication energy storage and the like.
With the expansion of the application field of lithium ion batteries, the requirements on the safety of the batteries are higher and higher. In order to improve the safety of a battery and simultaneously improve the wettability of a separator to an electrolyte, a coated separator in which high-temperature-resistant inorganic or organic particles are coated on the surface of a polyolefin separator has received increasing attention. Wherein the inorganic particles coat the separator with alumina Al 2 O 3 Ceramic coated membranes for coating are widely recognized and used.
However, the peeling strength of the conventional alumina ceramic coating diaphragm is greatly reduced after the diaphragm is soaked in the electrolyte, so that powder falling is easily caused, and a series of safety problems are caused. Meanwhile, with the popularization of power batteries, the requirement on the low thermal shrinkage performance of the diaphragm at high temperature is higher and higher.
Therefore, how to improve the high-temperature heat shrinkage performance of the ceramic coating diaphragm and solve the problems of reduced peeling strength, powder falling and the like of the ceramic coating diaphragm is a research focus of the ceramic coating diaphragm.
Disclosure of Invention
The object of the present application is to provide a novel ceramic coated separator and a method for preparing the same.
In order to achieve the purpose, the following technical scheme is adopted in the application:
one aspect of the application discloses a ceramic coating diaphragm, which comprises a base film and a ceramic coating coated on at least one surface of the base film, wherein the ceramic coating adopts a binder which is a two-component reaction type binder with the glass transition temperature of more than 120 ℃.
The ceramic coating diaphragm adopts the double-component reaction type binder with the glass transition temperature of more than 120 ℃ to prepare the ceramic coating, on one hand, a cross-linked network structure formed by the double-component reaction type binder can reduce the permeation and swelling of electrolyte to the binder, thereby maintaining the peeling strength to a greater extent; on the other hand, the high glass transition temperature of 120 ℃ or higher makes the adhesive maintain a certain mechanical strength at high temperature, so that the ceramic coating is not easy to deform. In one implementation of the present application, the peel strength of the ceramic coating membrane decreases by less than 30% after soaking in the electrolyte; the thermal shrinkage at high temperature is reduced by more than half compared with similar products; the safety of the lithium battery in the using process is improved.
Preferably, in the two-component reactive adhesive, the main component is at least one of polyacrylic acid and derivatives thereof, polyacrylate and derivatives thereof, and the secondary component is a crosslinking agent having two or more reactive functional groups which is crosslinked with the main component.
It should be noted that not all polyacrylic acid and its derivatives, and polyacrylate and its derivatives have a glass transition temperature of 120 ℃ or higher, but only polyacrylic acid and its derivatives, and polyacrylate and its derivatives having a glass transition temperature of 120 ℃ or higher are used in the present application. The two components of the binder are not directly related to the high glass transition temperature, the two components are overlapped to a certain extent, and the overlapped part is adopted as the binder; the high glass transition temperature is primarily a function of the choice of the monomers to be synthesized, for example, if the monomers contain more methacrylic acid or acrylamide, the glass transition temperature is relatively high.
It should be noted that the crosslinking agent used in the present application is used to link the main components by means of a crosslinking reaction, thereby forming a crosslinked network structure; therefore, the crosslinking agent needs to have two or more reactive functional groups. It will be appreciated that specific crosslinker types or reactive functionalities may be referenced to existing crosslinkers capable of crosslinking polyacrylic acid and derivatives thereof or polyacrylate and derivatives thereof, for example reactive functionalities selected from at least two of cyanate groups, hydroxyl groups, carboxyl groups, epoxy groups, amino groups, mercapto groups, aziridine tricyclic groups, carbodiimide groups, ester groups and derivatives of these reactive functionalities; the cross-linking agent is at least one of epoxy silane, isocyanate, pyridine, aziridine, polycarbodiimide, amino resin and resin with epoxy group.
Preferably, the ceramic material used for the ceramic coating is alumina powder, and the specific surface area of the alumina powder is less than 14m 2 The grain size of the alumina powder is more than or equal to 0.01 mu m and less than or equal to D50 and less than or equal to 10 mu m.
Preferably, the alumina powder has a particle size of 0.03 μm or more and D50 or less and 3 μm or less.
Preferably, the base film is a polyolefin microporous film, the thickness of the polyolefin microporous film is 5-20 μm, the porosity is 30% -60%, and the pore diameter is 0.005-0.15 μm.
Preferably, the polyolefin microporous membrane is a polyethylene microporous membrane, a polypropylene microporous membrane or a two-layer or multi-layer composite membrane formed by laminating the polyethylene microporous membrane and the polypropylene microporous membrane.
Preferably, the ceramic coating contains 0.5-10% of binder, 0-2% of dispersant, 0-5% of thickener and 0.05-3% of surfactant by total weight of the coating;
preferably, the thickness of the ceramic coating is 0.5-10 μm.
Preferably, the surfactant is at least one of an ethylene oxide polymer and a polyether polymer.
Preferably, the dispersant is at least one of sodium polyacrylate, ammonium polyacrylate, n-butanol, cyclohexanol and ethanol.
Preferably, the thickener is at least one of sodium carboxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl methyl cellulose.
The other side of the application discloses a preparation method of the ceramic coating diaphragm, which comprises the following steps,
(1) Weighing the components of the ceramic coating according to a proportion, and uniformly dispersing the components in deionized water to prepare ceramic coating slurry;
(2) And coating the ceramic coating slurry on one or two surfaces of the base film by adopting at least one of a scraper coating method, a Meyer rod coating method, a reverse roll coating method, a gravure roll coating method, a dip coating method and a brush coating method, and drying to obtain the ceramic coating diaphragm.
Due to the adoption of the technical scheme, the beneficial effects of the application are as follows:
according to the ceramic coating diaphragm, the ceramic coating is formed by the double-component reaction type binder with the glass transition temperature of more than 120 ℃, and the cross-linked network structure of the double-component reaction type binder can reduce the permeation and swelling of electrolyte to the binder, so that the peel strength of the ceramic coating diaphragm is improved; the high glass transition temperature of the glass transition temperature of more than 120 ℃ ensures that the adhesive can keep certain mechanical strength at high temperature, so that the ceramic coating is not easy to deform, and the high-temperature thermal shrinkage of the diaphragm is reduced. The ceramic coating diaphragm of the application solves the problem of powder falling of the ceramic coating and potential safety hazards caused by the powder falling of the ceramic coating, and improves the use safety of the lithium battery.
Detailed Description
Although the ceramic coating diaphragm can improve the physical strength of the battery diaphragm, the powder falling of the ceramic coating diaphragm is always a problem in the industry. The inventor of the present application starts with a binder to solve the problem of powder falling of the ceramic coating diaphragm, and in the prior patent application 201811637329.3 of the inventor of the present application, a two-component reaction type binder is used to reduce the reduction range of the peeling strength of the alumina ceramic coating diaphragm after being soaked in the electrolyte, so as to avoid the problem of powder falling caused by the reduction range. On the basis, the inventor of the application further intensively researches and discovers that the double-component reaction type binder with the glass transition temperature of more than 120 ℃ not only has the performance of reducing the permeation and swelling of electrolyte and keeping the peeling strength to a greater extent due to a cross-linked network structure; moreover, the high glass transition temperature enables the binder to maintain better mechanical strength at high temperature, so that the ceramic coating is not easy to deform; thereby having better high-temperature thermal shrinkage performance.
Based on the above research and recognition, the present application provides a novel ceramic coating separator, which comprises a base film and a ceramic coating coated on at least one surface of the base film, wherein the ceramic coating uses a two-component reactive binder with a glass transition temperature of above 120 ℃.
The ceramic coating diaphragm provided by the application continues previous research, creatively proposes to adopt the double-component reaction type binder with the glass transition temperature of more than 120 ℃, further improves the high-temperature heat shrinkage performance of the ceramic coating diaphragm, and solves the problems of reduced peeling strength, powder falling and the like of the ceramic coating diaphragm after being soaked in electrolyte.
The present application will be described in further detail with reference to specific examples. The following examples are intended to be illustrative of the present application only and should not be construed as limiting the present application.
Example 1
In this example, a two-component acrylic adhesive was used to prepare an alumina ceramic coated membrane having a specific surface area of 4.8m 2 The material is characterized in that the material is prepared from commercially available aluminum oxide with the D50 of 0.61 mu m, the base film is a 14 mu m single-layer PP film obtained from Shenzhen Zhongxing Innovation materials technology Limited, the porosity of the base film is 38%, and the pore diameter is 27nm. The preparation method of the alumina ceramic coating diaphragm comprises the following steps:
preparing a binder: the adhesive comprises a main component A of polyacrylic acid adhesive and a secondary component B of epoxy silane cross-linking agent, which are required to be added into the slurry respectively, wherein the weight ratio of A to B is 100. The glass transition temperature of the binder was 156 ℃.
Preparing slurry: mixing deionized water, alumina powder, a binder, a dispersant, a thickener and a surfactant according to a weight ratio of 70.6; wherein the dispersant is sodium polyacrylate, the thickener is sodium carboxymethylcellulose, and the surfactant is ethylene oxide polymer.
Preparing a ceramic coating diaphragm: and coating the prepared alumina slurry on one surface of the PP film by adopting a gravure roll method, wherein the coating speed is 70m/min, the drying temperature after coating is 60 ℃, and the coating amount is controlled to ensure that the final coating thickness is 2 mu m, so that the alumina ceramic coating diaphragm with the total thickness of 16 mu m is prepared.
The peel strength of the alumina ceramic coating diaphragm prepared in the example was tested by 180 degree peel strength test method, the width of the diaphragm sample was 20mm, and the diaphragm was continuously peeled by a tensile machine at 300 mm/min. The alumina ceramic coating diaphragm of the embodiment is soaked in the electrolyte for 24 hours at normal temperature, and then the soaked alumina ceramic coating diaphragm is measured by the same method. Wherein the electrolyte comprises 1mol/L LiPF 6 The solution is prepared from the following solvent in a mass ratio of EC to DMC to EMC of 15.
The test result shows that the peel strength of the alumina ceramic coating diaphragm prepared by the embodiment before soaking is 110N/m, and the peel strength of the diaphragm after soaking in the electrolyte is 90N/m; the peeling strength of the alumina ceramic coating diaphragm before and after the electrolyte soaking is reduced by 18.2 percent.
The thermal shrinkage ratio of the alumina ceramic-coated separator prepared in this example was measured after storing it at 150 ℃ for 1 hour, and the result showed that the thermal shrinkage ratio was only 2.5% after storing it at 150 ℃ for 1 hour.
The results show that the ceramic coating diaphragm of the embodiment has small reduction of the peeling strength after being soaked in the electrolyte, has low thermal shrinkage ratio at high temperature, can better improve the high-temperature thermal shrinkage performance of the ceramic coating diaphragm, and solves the problems of reduction of the peeling strength, powder falling and the like after the ceramic coating diaphragm is soaked in the electrolyte.
Example 2
In this example, polyacrylate was used as a main component of the binder in addition to example 1, and the polyacrylic acid in example 1 was replaced, and the glass transition temperature of the binder was 120 ℃.
A binder and a slurry were prepared in the same manner as in example 1, and an alumina ceramic coated separator of this example was obtained. The peel strength and the thermal shrinkage ratio of the alumina ceramic coating diaphragm of the present example were measured by the same method as in example 1; the alumina ceramic coating diaphragm of the present example was soaked with the same electrolyte and soaking method as in example 1, and then the peel strength of the alumina ceramic coating diaphragm of the present example after soaking was tested.
The results show that the peel strength of the alumina ceramic coating diaphragm of the present example before soaking was 109N/m, the peel strength after soaking in the electrolyte was 87N/m, and the decrease in peel strength of the alumina ceramic coating diaphragm before and after soaking in the electrolyte was small. The proportion of heat shrinkage after storage for 1 hour at 150 ℃ is only 2.6%.
Example 3
In the embodiment, on the basis of the embodiment 1, the dosage of the adhesive is optimized; the binder, alumina powder, base film, and other components of the alumina slurry used in this example were the same as in example 1, and the slurry preparation and ceramic coating membrane preparation were the same as in example 1, except that the binder was used in the following amounts:
test 1: deionized water, alumina powder, a binder, a dispersant, a thickener and a surfactant are mixed according to a weight ratio of 70.1;
test 2: deionized water, alumina powder, a binder, a dispersant, a thickener and a surfactant are mixed according to the weight ratio of 69.6;
test 3: deionized water, alumina powder, a binder, a dispersant, a thickener and a surfactant are mixed according to the weight ratio of (67.6);
test 4: deionized water, alumina powder, a binder, a dispersant, a thickener and a surfactant are mixed according to a weight ratio of 62.6;
adopting the alumina slurry of the four tests to respectively prepare four alumina ceramic coating diaphragms, and testing the peeling strength and the thermal shrinkage ratio of the four alumina ceramic coating diaphragms by adopting the same method as that of the embodiment 1; and soaking the four alumina ceramic coating diaphragms by adopting the same electrolyte and soaking method as in the embodiment 1, and then testing the peel strength of the soaked four alumina ceramic coating diaphragms.
The results show that the peel strengths of the alumina ceramic coating diaphragm of the test 1 before and after soaking are 109N/m and 90N/m respectively, and the thermal shrinkage ratio of the diaphragm after being stored for 1 hour at 150 ℃ is 2.6 percent; the peel strengths of the alumina ceramic coating diaphragm of the test 2 before and after soaking are respectively 112N/m and 94N/m, and the thermal shrinkage ratio is 2.4% after the diaphragm is stored for 1 hour at 150 ℃; the peel strengths of the alumina ceramic coating diaphragm of the test 3 before and after soaking are 113N/m and 97N/m respectively, and the thermal shrinkage ratio is 2.2% after the diaphragm is stored for 1 hour at 150 ℃; the peel strengths of the alumina ceramic coating membrane of the test 4 before and after soaking were 117N/m and 102N/m, respectively, and the thermal shrinkage ratio after storage for 1 hour at 150 ℃ was 2.1%.
The test results show that the peeling strength reduction range before and after the soaking of the alumina ceramic coating diaphragm is reduced along with the increase of the dosage of the adhesive; however, with the increase of the using amount of the adhesive, on one hand, the effect of reducing the peeling strength reduction range of the alumina ceramic coating diaphragm before and after soaking is stable; on the other hand, too much binder may also affect the ceramic properties of the alumina ceramic coating itself; therefore, it is considered that the amount of the binder is preferably 0.5% to 10% by analysis.
Comparative example 1
In this example, based on example 1, a one-component polyacrylic acid emulsion with a glass transition temperature of 4 ℃ was used as a binder, instead of the two-component reactive binder with a glass transition temperature of 156 ℃ in example 1, the other components, the amounts of the components, the slurry preparation and the ceramic coating membrane preparation were the same as those in example 1. This example also produced an alumina ceramic coated separator having a coating thickness of 2 μm and a total thickness of 16 μm.
The peel strength and the thermal shrinkage ratio of the alumina ceramic coating diaphragm of the present example were measured by the same method as in example 1; the alumina ceramic coating diaphragm of the embodiment is soaked by the same electrolyte and soaking method as those in the embodiment 1, and then the peeling strength of the soaked alumina ceramic coating diaphragm is tested.
The results show that the peel strength of the alumina ceramic coating membrane prepared in the example before soaking is 108N/m, the peel strength after soaking in the electrolyte is 40N/m, and the reduction range of the peel strength is 63%. The thermal shrinkage ratio after storage at 150 ℃ for 1 hour was 8.0%. As can be seen, the peel strength of the coated separator of this example decreased significantly after immersion in the electrolyte.
Comparative example 2
The adhesive is prepared by respectively adding a polyacrylic acid adhesive serving as a main component A of the adhesive and an epoxy silane cross-linking agent serving as a secondary component B of the adhesive into slurry, wherein the weight ratio of A to B is 50.
A binder and a slurry were prepared in the same manner as in example 1, and an alumina ceramic coated separator of this example was obtained. The peel strength and the thermal shrinkage ratio of the alumina ceramic coating diaphragm of the present example were measured by the same method as in example 1; the alumina ceramic coating diaphragm of the present example was soaked with the same electrolyte and soaking method as in example 1, and then the peel strength of the alumina ceramic coating diaphragm of the present example after soaking was tested.
The results showed that the peel strength of the alumina ceramic coated separator of this example before immersion was 107N/m, the peel strength after immersion in an electrolyte was 91N/m, and the peel strength of the alumina ceramic coated separator before and after immersion in an electrolyte was decreased. The thermal shrinkage ratio after storage at 150 ℃ for 1 hour was 6.0%.
As can be seen from the results of comparative analysis of the examples and comparative examples, compared with the single-component binder of comparative example 1, the two-component binder of comparative example 2 has a relatively small decrease in peel strength before and after the coating membrane is soaked in the electrolyte; the peel strength of comparative example 2 decreased by an amount comparable to examples 1 to 3; however, the coated separator of comparative example 2 was significantly inferior in heat shrinkage performance compared to examples 1 to 3 using a high glass transition temperature two-component binder. Therefore, the prepared ceramic coating diaphragm has the advantages that the peeling strength reduction range before and after the diaphragm is soaked in the electrolyte is obviously smaller, the heat-resistant shrinkage performance is obviously stronger, and the safety of the battery can be effectively improved.
The foregoing is a more detailed description of the present application in connection with specific embodiments thereof, and it is not intended that the present application be limited to the specific embodiments thereof. It will be apparent to those skilled in the art from this disclosure that many more simple derivations or substitutions can be made without departing from the spirit of the disclosure.
Claims (11)
1. A ceramic-coated separator comprising a base film and a ceramic coating layer coated on at least one surface of the base film, characterized in that: the adhesive adopted by the ceramic coating is a double-component reaction type adhesive with the glass transition temperature of 120 ℃;
in the two-component reaction type adhesive, the main component is at least one of polyacrylic acid and derivatives thereof, polyacrylate and derivatives thereof, and the secondary component is a cross-linking agent which has two or more than two reaction functional groups and is in cross-linking reaction with the main component.
2. The ceramic coated membrane of claim 1, wherein: the ceramic material adopted by the ceramic coating is alumina powder, and the specific surface area of the alumina powder is less than 14m 2 The grain size of the alumina powder is more than or equal to 0.01 mu m and less than or equal to D50 and less than or equal to 10 mu m.
3. The ceramic coated membrane of claim 2, wherein: the grain size of the alumina powder is not less than 0.03 mu m and not more than 3 mu m, and D50 is not less than 3 mu m.
4. The ceramic coated membrane of claim 1, wherein: the base film is a polyolefin microporous film, the thickness of the polyolefin microporous film is 5-20 mu m, the porosity is 30% -60%, and the pore diameter is 0.005-0.15 mu m.
5. The ceramic coated membrane of claim 4, wherein: the polyolefin microporous membrane is a polyethylene microporous membrane, a polypropylene microporous membrane or a two-layer or multi-layer composite membrane formed by laminating the polyethylene microporous membrane and the polypropylene microporous membrane.
6. A ceramic coated membrane according to any one of claims 1 to 5, wherein: the ceramic coating comprises 0.5-10% of binder, 0-2% of dispersant, 0-5% of thickener and 0.05-3% of surfactant based on the total weight of the coating.
7. The ceramic coated membrane according to any one of claims 1 to 5, wherein: the thickness of the ceramic coating is 0.5-10 μm.
8. The ceramic coated membrane of claim 6, wherein: the surfactant is at least one of ethylene oxide polymer and polyether polymer.
9. The ceramic coated membrane of claim 6, wherein: the dispersant is at least one of sodium polyacrylate, ammonium polyacrylate, n-butanol, cyclohexanol and ethanol.
10. The ceramic coated membrane of claim 6, wherein: the thickener is at least one of sodium carboxymethylcellulose, hydroxyethyl cellulose and hydroxypropyl methyl cellulose.
11. The method for preparing a ceramic coated membrane according to any one of claims 1 to 10, wherein: comprises the following steps of (a) preparing a solution,
(1) Weighing the components of the ceramic coating according to a proportion, and uniformly dispersing the components in deionized water to prepare ceramic coating slurry;
(2) And coating the ceramic coating slurry on one or two surfaces of a base film by adopting at least one of a scraper coating method, a Meyer bar coating method, a reverse roll coating method, a gravure roll coating method, a dip coating method and a brush coating method, and drying to obtain the ceramic coating diaphragm.
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| 离子聚合物胶体粒子增韧水性粘合剂 LA132 研究;马先果;《电源技术 研究与设计》;20180630;第778-781页 * |
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| CN111081956A (en) | 2020-04-28 |
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